Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length

Kamysbayev, Vladislav; Srivastava, Vishwas; Ludwig, Nicholas B.; Borkiewicz, Olaf J.; Zhang, Hao; Ilavsky, Jan; Lee, Byeongdu; Chapman, Karena W.; Vaikuntanathan, Suriyanarayanan; Talapin, Dmitri V.

doi:10.1021/acsnano.9b01292

Title: Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length

Journal Article · Tue Apr 09 00:00:00 EDT 2019 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.9b01292· OSTI ID:1558110

Kamysbayev, Vladislav ^[1]; Srivastava, Vishwas ^[1];

^[1]; Borkiewicz, Olaf J. ^[2];

^[1]; Ilavsky, Jan ^[2];

^[2];

^[2]; Vaikuntanathan, Suriyanarayanan ^[1];

^[3]

Univ. of Chicago, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

The nature of the interface between the solute and the solvent in a colloidal solution has attracted attention for a long time. For example, the surface of colloidal nanocrystals (NCs) is specially created to impart colloidal stability in a variety of polar and nonpolar solvents. This work focuses on a special type of colloids where the solvent is a molten inorganic salt or organic ionic liquid. The stability of such colloids is difficult to rationalize because solvents with high density of mobile charges efficiently screen the electrostatic double-layer repulsion, and purely ionic molten salts represent an extreme case where the Debye length is only similar to 1 angstrom. We introduce a detailed investigation of NC dispersions in molten salts and ionic liquids using small-angle X-ray scattering (SAXS), atomic pair distribution function (PDF) analysis and molecular dynamics (MD) simulations. Our SAXS analysis confirms that a wide variety of NCs (Pt, CdSe/CdS, InP, InAs, ZrO₂) can be uniformly dispersed in molten salts like AlCl₃/NaCl/KCl (AlCl₃/AlCl₄^-) and NaSCN/KSCN and in ionic liquids like 1-butyl-3-methylimidazolium halides (BMIM⁺X^-, where X = Cl, Br, I). By using a combination of PDF analysis and molecular modeling, we demonstrate that the NC surface induces a solvent restructuring with electrostatic correlations extending an order of magnitude beyond the Debye screening length. These strong oscillatory ion-ion correlations, which are not accounted by the traditional mechanisms of steric and electrostatic stabilization of colloids, offer additional insight into solvent-solute interactions and enable apparently "impossible" colloidal stabilization in highly ionized media.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; DMR-1420709; DMR-1611371

OSTI ID:: 1558110

Journal Information:: ACS Nano, Vol. 13, Issue 5; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 33 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
colloidal nanocrystals
ionic liquids
molecular dynamics simulations
molten salts
small angle x-ray scattering
solvent restructuring
x-ray pair distribution function

Title: Nanocrystals in Molten Salts and Ionic Liquids: Experimental Observation of Ionic Correlations Extending beyond the Debye Length

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